Azo-(2.3 hydroxy-naphthoyl)-aromatic diamines and azo dyestuffs derived therefrom



YPatented Aug. 16, 1932 nnNEsTr. Gnnlrrrna, or MIDLAND,mrcrrreainnssrsioaro 'rr-mrow CEEMICLCOM- Parry, or rfrrnLAivD,Mier-11am, njcoaroitn'rron' or 111:fortran1v'V THEREEROM lNo Drawing.Application filed .Tune 27,

My invention relates Vto new azo-arylamide derivatives of: V`2,3-hydroxy-naph thoic acid, as ywell as to direct-developed polyaz'odyestuifs derived therefrom by coupling with suitablediazotizedlorjtetrazotized aryl-amino compounds. V

In a pending application VSerial 'Nd 358,756, tiled Apri-l 27,'1929,"llhave' described certain new compounds 'comprising azoarylides of2,3-hydroXy-naphthoic acidfand azo dyestuts derived therefrom, t`helaforesaid aZo-arylides being formed by condensing a mono-amino-azocompound with 2.3- hydroXy-naphthoic acid in equimolecular proportion.VI have now found that compleX---aZo-arylides of related 4character maybe prepared by condensing anjazodiainine with 2 moles of2,3-hydroXy-naphthoic acid, the compounds Vso producedl constituting newand useful intermediate products from which azo dyes of excellentfastness tolight and washing may beprepared by couplin with suitablediazotized or tetrazotize arylamines.` The invention, then, consists ofthe aforesaid new intermediate compounds and azo dyestuffs derivedtherefrom, together with the methodsfor the preparation thereof, ashereinafter fully described and' particularly pointed outin the claims,the

following description setting forth detailed procedure representative ofvarious ways in which the used.

The vherein described new intermediate Compounds, comprisingpoly-(2,3-hydroXynaphthoyl) derivatives of mono-` or disaZo aromaticdiamines have the followinf eneral formula principle of the inventionmay beV q ing out the-'invention is -illustrated'in the fol- 192e.serial nemesi. f

ferries wherein X represents the residue of an'aromatic diamine,R anaryl residue or residues which maybe further substituted,- ,and 'n isthe integer Lor 2. When 'n is 2, R may represent either the same ordifferent arylresidues,

either one or both of which maybe further substituted .or not, asdesired, by vother monov valentigroups, such as halogen, nitro,l amino,y

azo groups, etc. and such substituent groups maybe substituted stillfurther when pos- Vsib-le. For example, an amino substituent group mayitself i be' substituted, as by alkyl, aryl or acyl groups. lTheaforesaid aromatic diamine' component may bev mono-nuclear, such asvphenylene diamine, vor Vmulti-nuclear, 1

'such as benzidine, diphenylene, etc., or y conA densedLnuclean suchvTas naphthylene diamine. l Thenewazodyestutt's are .prepared by cou-;pling .the Naforesaid' aXo-bis- (2,3-hydroxyynaphthoyl)V aromaticdiaminesiwith diazeftized'or tetrazotized arylamino compounds in theusual wav y,Said dyestufs dye cotton dire'ctly'ina wide rangel of colorsvarying "from orange to deep 'blue and black and in remarkably clear andbrilliant 'toneswhich arervery fast to light and washing. They areadvantageously applied by developingon the libre, but may also beproduced rin-substance or deposited'upon the usualsubstrata to'\formlakes, in which formstheylare useful l pigments. v b o i f 1Alprferred'mode of procedure for carrylowing specific eXamples,but itisunderstood thatisuch examples are not to be Vinterpreted asta limitationupon theivinventi'on.

; Emamplcl 2 moles meta-nitraniline are diazotized and coupled withlniole meta-phenylene diamine. VThe disazo-diamine product is `thencondensed with`2 moles '2,3jhydroxy-V -r,n iphthoic,acidjby heating thetwo compounds f ing point, with addition of a small amount of if`Insimilar manner to Example-Lione phosphorus trichloride, the heatingbeing carried out under reflux for from 3 to 5 hours.

The reaction product is then neutralized With sodium carbonate and thetoluene distilled olif with steam. The desired compound, bis- (metanitrobenzene) disazo bis (2,3 hymole 'the resultant azo-diamine iscondensed with two moles 2,3-hydroXy-naphthoic acid. rlfhe intermediateproduct so prepared is then coupled on the fiber With 2 molesalpha-naphdroXy-naphthoyl) meta-phenylene-diamine, .a

remains in suspension in the residual aqueous N=N`| VN=N solution, andis liltered therefrom i and Y /QH p HO v Washed With Water. The productis purified Y Y* by dissolving in dilute, 1 to 2 per cent., caustic Yalkali solution,. iltering from l`unreacted.-v VCONEK IIHOC v t ydisazo-diamine and reprecipitating by acidi-'o Y s Q ication of thealkaline solution. The intermediate compound so produced has the N=Nf001ff formula.; y' n l f j L Y. e -A t Emmmple /on y y Ho\ er l Y a vl' 'y r I' Y 11molelapha-Iaphthylamine il'dialzotizd L f Y' Y l an couAe Wit l mo e metaen ene i- 2i I K I ooNHO/NEOG amine, tphe azodianiineis conoensed7 with 2 moles 2,3-hydroXy-naphth0ic acid and the a @-N--Nbsx-Q intermediateproduct so formed is coupled on Y 1 i K the liber With1 mole dianisidine. -The color 30 N0? i n N01 is Va yclear shade ofblue. The dyestui has t Y i 1 probably the formula; p CottonV materialis impregnated with a i Y slightly alkaline solution of the aboveinter-Y cHao 00H,

p mediate compound to which a small amount 'f Y i Y v .of formaldehydemay be advantageously Tdi-O N?? added andyf desired, Turkey red oil orother /oH Ho f -agentV to `i'acilitate the absorption ofthe compound bythe fiber. The impregnated matel \A .,A rial. is then immersed lina coldsolution of J 'CONH NHOC 40 sodiumacetateor carbonate and the dye devveloped by adding a diazo solution prepared from 2 molesmeta-nitraniline; The color is Y N=`N Y a bright orange-salmon.Thedyestuif has Y /OH- K E0 a A y coNH NHoo 1 y i ,1 NO2 Y NO2 eo fExample? Eample l mole para-amino-acetanilide is diazotized ipara-phenetidine is diazotizfedv and coupled .and coupled With 1.1nolemeta-phenylene di- With one mole meta-phenylelle diamine Vand. amin- Theacetyl group is removed by safgsfflms n 3 4 @niyingi and "the :resultant*triaminoiconipelmd scondensle with 3'1110lS'2-hydr0xyn'apht'boic acid.Thentermedite compound resulting from such condensationis` 'then cou-4pled on the iberwlith 3 'moles 'parra-unino- ,acetni1ide, the colorbeing fu clear., light/'rose- ,pinkb The -dyestuff lhas probably vtheformulas l l mole benzidine is tetrzotized and cou- 25 .pled with 2moles meta-phenylene diamine afnd the product Acondensed with 4 moles,2,3- lbydrczy*niphtluoic acid. The intermediate product so formed'isthen coupled on the ber with L Vmoles l-ainino-naphthyl--phenyl i3@ether, the color being a medium Shade of lavender-Yiolet. The dyestuffhas probably the formula;

v E HO\ "XON iNnoC/Ii coupled Withl mole Lfnaphtbylene. diamine 'Y andthelproduct condensed-Withmoles2,3- hydroXy-,naphthoic acid. Theintermediate 60 product is then coupled'ion the 4fiber With-i2 molesortho-aminodiphenyl Lether, the colordeve-oped--being-a-brighteosinepink lt is to be noted'that the latterdye shows an especiallyistrong Vaffinity `for synthetic*nitro-celluloseY 85 bers, such as rayon.

Arylide component t I n l t v Diazo component Color 'Diazo compound of-Coupled With- Ifroduct condensed with- I 1 2 moles -nitranilineL-phenyienediamine 2 moles 2,31iydroxy-naph- 2-ch10r-V4-nitraniline Redorange 2 moles 3nitrani1ine 1,3-pheny1ene diamine 2ifiglsac-hydroxy-naph- 2-amino-dipheny1 ether Pink 1 mole 3-11itrani1ine1,3-pheny1ene diamine 2 ifiglgsacB-hydroxy-napb -4-amino-acetani1ideViolet red 1 mole B-nitraniline 1,3pheny1ene diamine 2iikigls-hydroxy-naph- -naphthylamine Red violet 1 mole 4-phenetidineL'-pnenylenediamine 2 itrlilglisac-liyrdroxy-naph-l 3, 4-dieh1orani1inet l'etenna red 1 mole 4phenetidine 1,3-pheny1ene diamine k2itililiesacS-hydroxy-naph- 2nitro4phenetidine I Bordeaux 1mole-naphthylamine LB-phenylene diamine 2 tglesctS-hydroxy-naph-`lfrphvevinylene diamine Henna red l'mole-naphthylamine 1,3-pheny1enediamine 2 glifsaciZS-hydroxy-naph- 4,4diamino diphenyi ether Carmine 2moles 4-phenetidine 1,3-pheny1ene diamine 2` moles2,3-hydroxy-naphbenzidine Red violet 2 moles 4phenetidine 1,3-pheny1enediamine 2 ffigigsamf-hydroxy-napb 2,- nitro-4-phenetidineazo- Dark gray2 moles-naphthylamne 1,3-pheny1ene diamine 2ifilglgsacZfIi-hydroxy-naph-H 2-dvldjr-)Bidllli Red v t' 2moies-tnaphthylamine 1,'3-pheny1ene diamine 2glieli;lis(lZB-hydroxy-naph-I 1-pheny1-25anisidine Magenta 2 moles-ntraniline 1,5-naphthy1ene diamine 2 icililgiisahydroxy-naph-S-nitraniline t Orange 2 moles S-ntraniline 1,5-naphthyiene diamine 2mglsaciZB-hydroxy-naphl-rilielo-Ynaphthyl--phenyl Lavender 2 moles3nitraniline 1,5-naphthy1ene diamine 2 rkilglisact-hydroxy-napb dianisidine DarkY blue 2 moles 3-nitraniline 1,5-naphthy1ene diamine 2moles 2,3-hydroxy-naph- 3ntrobenzeneazo -naph- Violet 1k mole benzidine(2)l 1,3-pheny1ene diamine 4 higigsacS-hydroxy-naph- 2ctiilsrfrlifi1ani1ine Copper red 1 mole benzidine (2) 13-pheny1ene diamine 4itilihlli51(dl-hydroxy-naph-N 2-amino-dipheny1 ether Scarlet 1 molebenzidine (2) 1,3-pheny1ene diamine 4trlilgisacizS-hydroxy-naphdianisirdine v Blue Y 1 mole benzidine (2)1,3-pheny1ene diamine 4 pilziezsagLhydroxy-naph- 4niittpbeniene az-o- 2-toiui- Reddis'n nrown 1 mole 4-amino-aeetan1ide 1,3-pheny1ene diamine 3llpiisacmydroxymaph- `BfnitranilinxaV t Salmon 1 mole4-amino-acetani1ide 1,3-pheny1ene diamine rtxlillliesaI-hydroxy-naph--naphthylamine YPink 1 mole 4-amino-acetanilide 1,3pheny1ene diamine 3moles 2,3hydroxynaph 4 -phenetolazo naphthyl- Gray thoic acid aminetetrazotized arylamino compounds With the not'only theneW dyestuifs ofthe'general type The dyestuff has probably the formula;

/o oNH Nie-O fibers of vegetable origin.

In similar fashion other dyestuffs l may be prepared by coupling otherdiazotized or diamines.V The components Yemployed* for, and the colorsyproduced by, several'ofsuch similar dyeings are given in the accompany-Vlng table. Y

Although in' the detailed' Example l the cotton fiber is specificallyreferred toas a material' upon. Whichthe present dyes may be vdeveloped, my new dyestuifs are also capable of dyeing other natural orsyntheticbers, such as silk and rayon, or the like, specific referenceto such latter application being made in EXampleG above. It isfurthermore to be noted that, in contra-distinction to the general classof substantiative dyestuifs, the dyestuifs of the vpresent invention arealso Well adaptedy for dyeing Wool fibers, the resulting dyed lproductspossessing equal fastness to thoseproduced upon cotton or similar Thepresent-dyestuifs may be applied by developing on the berdor not, asdesired, the invention being independent of the particular mode ofapplication employed. VAuxiliary treatments for fixing or for aiding theabsorption of the dyestu" by the iber'may be utilized optionally*y inconnection with the dyeing process Without departing from the spirit ofthe-inventionl'vvhich comprehends 5 same or other poly- (2, 3

derivatives of mono-azo- -hydroXy-nap hthoyl) herein described but alsor disaZo-aromatic therewith.

o, materials dyed igea-151s' Infcarrying outthe inventionfor` produclingA the :present new azo dyestuiis, the A:result is, of course,equivalent whethertwo; moles of a ldiazotized aryl-'mono-amine or onemole coupling with an intermediate product derived from2,3-hydroxy-napvhthoi/c acid of the type herein described.

Other mod-es 01E-applying the principle of my invention may be employedinstead of the one explained, change being made as regards the steps ormaterials employed, provided the stepsor-ingredients statedv byv any ofthe following claims or the equivalent of such stated steps oringredients beemployed` therefore particularly point out and distinctly.claim as my invention i 1. The method of making a new azo com poundwhich comprises coupling any diazotizd aromatic amine of the benzene,naph-v thalene or diphenyl series with an aromatic diamine or the (groupconsisting of the benzene, naphthalene, diphenyl, and ldiphenyleneserie'siand condensing the thereby formed azo-diamine with twolAolecularV equivalents of 2.3"-hy'droxynaphthoicacid; Y

2. The method of making a new azo dye which comprises coupling any:diazotized aromatic amine of the benzene, naphthalene orfdiphenyllseries with an aromatic diamine of the group consisting of thebenzene,naphthalene, diphenyl, and diphenyle'ne series, condensing thethereby formed azo-diamine with two molecular equivalents lof2.3-hydroxynaphthoic acidjand. then coupling the obtained intermediatecompound with a diazotized aromatic amine.,` l n 3. As a new compound,the condensation product of an azo-aiomatic-diainine with 2 molecularequivalents of 2,3-hydroXy-naplithoic acid, having the general formula;

@/OH H0\ Y l Y \ooNH Miou@ l in which X is the residue of an aromaticdiamine of the benzene, naphthalene, diphenyl, and diphenylene series, Ris an' aryl residue of the benzene., naphthalene, or diphenyl serieswhich may be further substituted by one or more of the following groupshaloamino and an aryl-azo group of the benzene or naphthalene series,and wherein n represents the integer l 0r 2.

4. As new compounds, the condensation S5-product of adisazo-aromatic-diamine with of a tetrazotize'd diamine-are employedfory 2v lmolecula'r; equivalents of `2,3-'hydroxyf-n i naphthoic acid,having thegeneral formula-;

i s 05H. i HOV i i y foon 'NHoc' inlwhich iX is the'residue of anaromatic'di-amine of the benzene, naphthalene, diphenyl, an diphenyleneseries and R and R are aryl residuesoi'. the benzene, vnaphthalene, or

diphenylvseries which may be further, substi# tuted by `one or more. ofAthe following groups halogen, nitro, alkoxy, 2-hydroXy- 3-naphthoylaminoand an aryl-azo Vgroup of the benzene or naphthalene series.

5. As anew compound,` the condensation product of an aZo-meta-phenylenediamine with 2 molecular equivalents of 2,3-hydroxynaphthoic acid,having. the general formula;

V\ooNH s Y NHoo` g Y R.N=N y in whichltis lan aryl residue of thebenzene, naphthalene, or diphenylseries which may bel furthersubstituted by one 0r more of the following groups :-halogen,nitro,alkoXy, 2- hydr'cxyf-naphthoylamino and an aryl-azo group Vofthe benzeneor naphthalene series, and wherein n represents the integer ll or 2.

6. As. a new compound, the condensation product of adisaZo-meta-phenylene diamine with 2 molecular equivalents of2,3-hydroXynaphthoic acid, having the general formula mesi' ,Y in whichX5 is the residue of an aromatic groupsAz-halogen,

llO

diamine of .-theabenzene, 'naphthalene, diphnyl or diphenylene series,VR visfan aryl residue of the benzene, naphthalene or diphenylserieswhich may be further substituted by one. or more of the following groups:-halogen', nitro, alkoXy,*2-hydroxy S-naphthoylamino and an aryl-azogroup of the benzene or naphthalene series, and wherein fn is theinteger1 or 2, and Y is' theresidue ofV` a tetrazotized aromatic diaminecompound. 1

8.,As a new compound, an azo dyestuff i having probablythe generalfor-mula;

in'which R is an aryl residue of the benzene, naphthalene, or diphenylseries which may be further substituted by one or more of the followinggroups :--halogen, nitro, alkoxy, 2-hydroxy-3-naphthoylamino andV an'arylazo group of the benzene or naphthalene series, and in which n isthe integer 1 or 2, said group being coupled with a diazotized aromaticamino compound.

10. As a new compound, an azo probably the general formula,

dye having wherein X represents the residue of an matic diamine of thegroup consisting of the benzene, naphthalene, diphenyl, and diphenyleneseries, R represents an aryl residue of the benzene, naphthalene ordiphenyl-*series which maybe further substituted by one or more of thegroups halogen, nitro, alkoxy, 2-hydroxy-S-naphthoylamino and anarylafzo group-,of the benzeney or naphthalene searo- Y ries, Zrepresents. the residue. of aldiazotized aromatic amino compound, vandwherein fn;

is the integer 1 or 2.

A 11. As a new compound, an a-zo dye having probably the general.formula,

wherein R represents yan aryl' residue of the`v benzene, napthalene ordiphenyl series which may be furtherv substituted by one or moreof thefollowing groups :-.-h'alogen, nitro,- alkoXy,2-hydroXy-3-naphthoylamino and*r an aryl-azo group of the benzene ornaphthalene series, Z represents the residue of a diazotized aromaticaminoeompound'and whereinv n is the integer l or 2. Y

`12. As a new compound, an azo dyestu characterizedbythe group in whichR is an aryl residue of the benzene, naphthalene, or diphenyl serieswhich may be further substituted by one or more ofthe following Vgroups.:-halogen, nitro, alkoxy, 2-hydroXy3-naphthoylamino and an arylazo Ygroup of the benzene` or naphthalene series, and in which n is'V theinteger 1 or 2,

' -oH i no- L v -GONHQJINOG said group being coupled with al diazotized'105 aromatic. amino compound. l e Y Signed by'me this 24th day of June,1929.

ERNEST" F. GRETHER.

